Preparation of substituted pyridines

ABSTRACT

Substituted pyridines are prepared by reacting an ethylenically unsaturated hydrocarbon, carbon monoxide, hydrogen and ammonia in a liquid medium containing a Group VIII noble metal catalyst in complex association with a biphyllic ligand at a temperature of 50* to 400* C. and a pressure of 5 to 300 atmospheres. A typical process comprises contacting ethylene, carbon monoxide and hydrogen with a liquid reaction medium containing ammonium hydroxide, rhodium trichloride and triphenylphosphine to produce 3,5-dimethyl, 2-ethyl pyridine.

United States Patent Fenton [451 July 25, 1972 [54] PREPARATION OFSUBSTITUTED PYRIDINES [72] Inventor: Donald M. Fenton, Anaheim, Calif.

[73] Assignee: Union Oil Company of California, Los Angeles, Calif.

[22] Filed: April 23, 1970 [2]] Appl. No.: 31,371

Related U.S. Application Data [63] Continuation-impart of Ser. No.637,891, May 12,

1967, abandoned.

[52] U.S. (I 260/290 P [51] Int. Cl. ..C07d 31/06 [58] Field of Search..260/290 [56] References Cited UNITED STATES PATENTS 3,463,781 8/1969Bell et a1 ..260/290 Primary ExaminerHenry R. .liles AssistantExaminer-Harry l. Moatz Attorney-Milton W. Lee, Richard C. Hartman,Lannas S. Henderson and Robert E. Strauss [5 7] ABSTRACT Substitutedpyridines are prepared by reacting an ethylenically unsaturatedhydrocarbon, carbon monoxide, hydrogen and ammonia in a liquid mediumcontaining a Group VIII noble metal catalyst in complex association witha biphyllic ligand at a temperature of 50 to 400 C. and a pressure of 5to 300 atmospheres. A typical process comprises contacting ethylene,carbon monoxide and hydrogen with a liquid reaction medium containingammonium hydroxide, rhodium tn'chloride and triphenylphosphine toproduce 3,5-dimethyl, 2-ethyl pyridine.

13 Claims, No Drawings PREPARATION OF SUBSTITUTED PYRIDINES Thisapplication is a continuation-in-part of application, Ser. No. 637,891,now abandoned.

DESCRIPTION OF THE INVENTION This invention relates to the preparationof hydrocarbon substituted, particularly alkyl substituted, pyridines.More particularly, the invention relates to preparation of suchpyridines by reaction of an ethylenically unsaturated hydrocarbon withcarbon monoxide, hydrogen and ammonia in the presence of a complex noblemetal catalyst.

The products of the reaction are useful raw materials for the productionof various pharmaceuticals such as sulfonarnides, antihistamines, etc.,and for other useful chemical products such as surfactants and solventsfor synthetic resins. They are also useful as solvents and catalysts forcertain organic reactions. The products of the process have the generalformula:

Prior art patents such as U. S. Pat. Nos. 2,935,513; 4

2,963,484; and 2,995,558 disclose preparation of pyridine or substitutedpyridines by reaction of aldehydes, alcohols, acetylenic compounds,etc., with ammonia. However, the present invention has the distinctadvantage of preparation of the substituted pyridines from basic andeconomical raw materials.

According to the invention, the substituted pyridines are prepared byreacting an ethylenically unsaturated hydrocarbon, carbon monoxide,hydrogen and ammonia in a liquid reaction medium containing a Group VIIInoble metal-containing catalyst in complex association with a biphyllicligand, all to be defined hereinafter.

The ethylenically unsaturated hydrocarbon reactant has two to about 24carbons, preferably 2 to about 18 carbons and has the following formula:

wherein R,, R R and R, are hydrogen or the same or different alkyl,cycloalkyl or aryl, preferably alkyl; or

wherein one of said R and R groups together with one of said R and Rgroups together form an alkylene group resulting in a cycloalkene having4 to 10 cyclic carbons.

As used herein, the terms alkyl, cycloalkyl and aryl include hydrocarbylgroups wherein the radical carbon of the group is in an alkyl,cycloalkyl or aryl group and thus includes groups such as aralkyl,alkaryl, alkylcycloalkyl, etc., as well as purely alkyl, cycloalkyl andaryl groups. Examples of alkyl groups therefore include ethyl, benzyland phenylhexyl; examples of cycloalkyl include cyclohexyl andmethylcyclopentyl; and examples of aryl include phenyl andp-dodecylphenyl. The particular hydrocarbyl group is not the essence ofthe invention since the functional carbons are the carbons forming theolefinic double bond.

Examples of useful unsaturated hydrocarbons are propylene, butene-l,butene-2, pentene-Z, Z-methylbutene-l hexene-l, 3-ethylhexene-1,octene-3, Z-propylhexene-l, decene-2, 4,4'-dimethylnonene-l, dodecene-l,6-propyldecene-l, tetradecene-S, 7-amyldecene-3, hexadecene-l, 4-ethyltridecene-Z, octadecene-l, 5,5-dipropyldodecene-3, eicosene-7,cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, cyclooctene,cycloheptene, l,4-dibutylcyclohexene, 3-cyclohexyldecene-2,vinylcylohexane, allylcyclohexane, styrene, p-methylstyrene,alpha-methylstyrene, beta-methylstyrene, p-vinylcumene,beta-vinylnaphthalene, l ,Z-diphenylethylene, allylbenzene,6-phenylhexene-l 1 ,Bdiphenylbutenel 3-benzoheptene-3, o-vinyl-p-xylene,divinylbenzene, l-allyl-4-vinylbenzene, 2,6-diphenyloctene,5-butyl-7-cyclohexyl-nonene-2, 3-toIyl-4-ethyldodeccne-7, etc. Of thesethe aliphatic hydrocarbon olef'ms having from about two to 18 carbons,e.g., ethylene, butene, dodecene, etc., are preferred and most preferredare the alpha alkenes having terminally unsaturated carbons e.g.,butene-l, octenel, decene-l etc.

The catalyst employed of the invention is a Group VIII noble metal whichis preferably in complex association with a biphyllic ligand ofphosphorus, arsenic or antimony to be defined hereinafter.

The Group VIII noble metal can be palladium, rhodium, ruthenium,platinum, osmium or iridium. While catalysts containing any of thesemetals are active for the reaction, I prefer to employrhodium-containing catalysts because of their demonstrated greateractivity, particularly at the relatively mild reaction conditionsemployed for the reaction. A catalytic quantity of the Group VIII noblemetal-containing catalyst is used. This is generally an amountsufficient to provide a concentration of the Group VIII noble metalwhich is between about 0.001 and about 5.0 weight percent of the liquidreaction medium and preferably between about 0.001 and about 0.5 weightpercent. The Group VIII noble metal can be added to the reaction mediumas a soluble salt, an acid, an ammino, halo, hydride, or carbonylcomplex, or as the elemental metal. The particular form in which themetal is added is not critical since in all cases, it forms a complexwith the biphyllic ligand.

Examples of suitable salts are the nitrates, halide, hydroxides,cyanides, sulfates, sulfites, carbonates, C -C carboxylates, etc., ofthe metals such as rhodium nitrate, platinum nitrate, palladiumchloride, rhodium fluoride, palladium hydroxide, platinum cyanide,osmium sulfate, rhodium sulfite, rhodium carbonate, palladium carbonate,platinum propionate, rhodium acetate, etc. Examples of suitablecomplexed sources are rhodium carbonyl, ruthenium pentacarbonyl,diamrninepalladium hydroxide, tetramminepalladium tetrachloropalladate,tetrachlorodiammine platinum, aquopentammine iridium chloride,nitratopentammine iridium nitrate, palladium acetyl acetonate,hexachloropla tinic acid, tetracyanoplatinic acid, potassiumhexachloroplatinate, ammonium tetracyanoplatinate, etc. The carbonyl ofthe Group VIII noble metal can be prepared externally and introducedinto the reaction medium or the carbonyl compound can be produced insitu by the addition of the Group VIII noble metal and introduction ofthe carbon monoxide during the reaction to form an active carbonylcomplex.

The biphyllic ligand which is in complex association with the Group VH1noble metal is a compound having an element with a pair of electronscapable of forming a coordinate bond with a metal atom andsimultaneously having the ability to accept the electron from the metal,thereby imparting additional stability to the resulting complex.Biphyllic ligands can comprise organic compounds having at least aboutthree carbons and containing arsenic, antimony or phosphorus in atrivalent state. Of these, the phosphorus compounds, i.e., thephosphines, are preferred; however, the arsines and stibines can also beemployed. The biphyllic ligands are well known in the art and in generalhave the following structure:

wherein E is a trivalent atom selected from the class consisting ofphosphorus, arsenic and antimony; and

wherein R is a member of the class consisting of hydrogen, alkyl havingone to 10 carbons, cycloalkyl having four to 10 carbons, aryl having sixto 10 carbons, and halo, amino and alkoxy substitution products thereof;and

wherein R is alkylene having from one to about eight carbons.

Examples of suitable biphyllic ligands having the aforementionedstructure and useful in my invention to stabilize the catalystcomposition are the following: phenylphosphine, propylarsine,diphenylstibine, diethylphosphine, dioctylarsine, methylpropylphosphine,trimethylphosphine, triethylarsine, triisopropylstibine,triaminobutylarsine, ethyldiisopropylstibine, tricyclohexylphosphine,triphenylphosphine, tri(otolyl)phosphine, phenyldiisopropylphosphine,phenyldiamylphosphine, diphenylethylphosphine,tris(diethylaminomethyl)phosphine, tritolylbismuthine,ethyldiphenylphosphine, phenylditolylphosphine,cyclopentyldixylystibine, dioctylphenylphosphine, ethylenebis(diphenylphosphine), hexamethylene bis(diisopropylarsine),pentamethylene bis(diethy1stibine), etc. Of the aforementioned, the arylphosphines, particularly the triarylphosphines, e.g.,triphenylphosphine, are preferred because of their demonstrated greateractivity for stabilization of catalysts.

The catalyst may be complexed with the above-described biphyllic ligandbefore being introduced into the reaction medium or the complex may beformed in situ by simply adding the metal and the biphyllic liganddirectly into the reaction medium. In either case, it is generallypreferable that the quantity of biphyllic ligand be in excess, e.g.,10-300 percent of that stoichiometrically required to form a complexwith the metaland is generally 0.002-10 weight percent, preferably0.002-2 percent of the reaction medium. The complex has from 1 to about5 moles of biphyllic ligand per atom of the metal and other componentssuch as hydride, or soluble anions such as sulfate, nitrate,carboxylates, (e.g., acetate, propionate, isobutyrate, valerate, etc.),halide, etc. may be but need not be included in the complex catalyst ofthis invention. These components may be incorporated in the catalyst bythe formation of the catalyst complex from a metal salt of the indicatedanions. A preferred complex is one comprising at least one halide orcarboxylate, ligand, e.g., chloride, bromide, iodide, fluoride, acetate,propionate, butyrate, benzoate, etc., since these groups, particularlythe halides, improve the activity of the catalyst.

As a preferred embodiment the reaction medium also contains a poly(heterocyclic) saturated amine, preferably a hi or tri (heterocyclic)saturated hydrocarbon amine, having at least one nitrogen in abridgehead position. The term bridgehead position is well established inchemical nomenclature to identify the position of an atom which iscommon to at least two of the rings of the polycyclic compound.Preferably the amine is an atom-bridged system, i.e., atoms, generallymethylene carbons, form the bridge or line in the molecule rather than asimple valence bonding. The amine is used in catalytic amounts, e.g.,from about 0.001 to about weight percent, preferably from about 0.05 to5 weight percent, of the liquid reaction medium. In general, amineshaving from one to about four nitrogen, preferably one or two nitrogens,and from one to about 25 carbons, preferably from two to about 10carbons, can be employed for this purpose, the most preferred being thebi(heterocyclic) saturated hydrocarbon amines having one or twonitrogens and four to 10 carbons. The following is a listing ofrepresentative amines useful in my invention: l,2,4-triazabicyclo(l.l.l)pentane; 1,5 ,6-triazabicyclo( 2. l l )hexane;5oxa-1,6-diazabicyclo(2.l.1)hexane; 5-thia-1,6-diazabicyclo(2.l.l)hexane; 2-oxa-l,5,6-triazabicyclo(2.1.1)hexane;

l-azabicyclo( 2.2. l )hept ane; l-azabicyclo( 3.3.1 )heptane;

ane; 1,4-methano-l, l-pyridine; 2-ox-1azabicyclo(2.2.l)heptane; l,4-diazabicyclo( 2.2. l )heptane; 7-oxa- 1-azabicyclo( 2.2.1 )heptane;7-thia-l-azabixyxlo(2.2. l )heptane; 1,7- diazabicyclo( 2.2.1 )heptane;l,3,5-triazabicyclo(2.2.1)heptane; l-azabicyclo(3.2. l )octane;l,5-diazatricyclo(4.2. l )d ecane; 'l,7-diazatricyclo(3.3.l.2) undecane;7-ox-lazabicyclo(3.2.l)octane; l,7-diazabicyclo(3.2.l)octane;3-thial,7diazabicyclo(3.2.1)octane; 1,3,6,8- tetrazatricyclo(6.2. lldodecane; 2,8-diazatricyclo(7.3. l .l

tetradecane; l-azabicyclo(3.3.l)nonene, also known as 1-1,2,5,6-tetrazabicyclo(2. 1.1 )hexane;5-oxa-l,2,3,6-tetrazabicyclo(2.1.1) hex-.

isogranatinine and the oxo,hydroxy and lower alkyl derivatives thereof;l-azabicyclo(2.2.2)octane also known as quinuclidine as well as thehalo, oxo, hydroxy and lower alkyl derivatives thereof; l-azatricyclo(3.3.1.1 )decane; 1,3-diazabicyclo(2.2.2)octane; 1,3-diazabicyclo (3.3.1 )nonene; 1,6- diazatricyclo( 5.3. l l )dodecane; 2-oxl -azabicyclo(2.2. 2)octane; 4,6,10-triox-l-azatricyclo(3.3.l.l)decane;1,5-diazabicyclo(3.3. l )nonene; l,2,5,8-tetrazatricyclo( 5.3. l l)dodecane; l,4-diazabicyclo(2.2.2)octane also known as triethylenediamine and its oxo, hydroxy, halo and lower alkyl derivatives thereof;1,3-diazatn'cyclo( 3.3.1.1)decane also known as 1,3-diazaadamantane;l,3,5-triazatricyclo( 3.3. l )d ecane; l,3,5,7-tetrazabicyclo(3.3.l)nonene also known as pentamethylene tetramine;l,3,5,7-tetrazatricyclo(3.3.1.1) decane also known as hexamethylenetetramine; 2-oxa-l,3,4- triazabicyclo(3.3.l)nonene; l-azabicyclo(4.3.l)decane; lazabicyclo( 3.2.2)nonene; l,5-diazabicyclo( 3.2.2)nonene; l,3,5,7-tetrazabicyclo( 3.3 .2)decane; 1,5-diazabicyclo3.3.3)undecane; etc.

Of the aforementioned poly(heterocyclic) amines having a nitrogen in abridgehead position the most common and widely known compounds isl,4-diazabicyclo(2.2.2)octane, known as DABCO, and this material as wellas its oxo, hydroxy, halo and lower alkyl derivatives comprises thepreferred amine for use in my process.

The reaction is performed under liquid phase conditions which may behydrous or anhydrous; however, better yields are usually obtained ifwater is present. The reaction solvent may be water, concentratedammonium hydroxide, or an organic solvent or mixtures thereof. Anyconventional organic solvent, which is inert to the reactants, thecatalyst, the products and the reaction conditions may be used. Examplesof suitable solvents that can be used in accordance with my inventioninclude hydrocarbons such as the aromatics,

aliphatics or alicyclic saturated hydrocarbons, ethers, esters, ketones,alcohols, etc.

Examples of suitable solvents include benzene, toluene, xylene,ethylbenzene, tetralin, etc.; butane, pentane, isopentane, hexane,isohexane, heptane, octane, isooctane, naphtha, gasoline, kerosene,mineral oil, etc.; cyclopentane, cyclohex-' ane, methylcyclopentane,decalin, indane, diisobutyl ether, din-butyl ether, ethylene glycoldiisobutyl ether, methyl o-tolyl ether, ethylene glycol dibutyl ether,diisoamyl ether, methyl ptolyl ether, methyl m-tolyl ether,dichloroethyl ether, ethylene glycol diisoamyl ether, diethylene. glycoldiethyl ether, ethylbenzyl ether, diethylene glycol diethyl ether,diethylene glycol dimethyl ether, ethylene glycol dibutyl ether,ethylene glycol diphenyl ether, triethylene glycol diethyl ether,diethylene glycol di-n-hexyl ether, tetraethylene glycol dimethyl ether,tetraethylene glycol dibutyl ether, ethanol, propanol, butanol, t-butylalcohol, t-octyl alcohol, sec-pentyl alcohol, benzyl alcohol, etc.

The process may be conducted in the absence of solvent by providing anexcess, e.g., 30-100 percent in excess of that stoichiometricallyrequired, of the olefinic reactant if such is a liquid, or such anexcess of the ammonia reactant if supplied as liquid ammonia or ammoniumhydroxide. A preferred reaction medium is concentrated ammoniumhydroxide.

The reaction is performed under relatively mild conditions includingtemperatures from about 50 to about 400 C.; preferably from about 70 toabout 200 C. Sufficient pressure is used to maintain the reaction mediumin liquid phase. Although atmospheric pressure can be used, the rate ofreaction is increased by superatmospheric pressures and, therefore,pressures from about 5 to about 300 atmospheres absolute and preferablyfrom about 10 to about atmospheres are used. The ratio of the reactantscan be widely varied if desired but preferably the molecular ratio ofhydrogen to carbon monoxide is from about 1:10 to about 10:1. Thereaction is exothermic and the temperature can be maintained by suitablecooling of all or a portion of the reaction zone contents. The pressurescan be maintained by the pressure of the gases supplied to the reactionzone. If desired, a suitable inert gas,

such as nitrogen, can also be charged to the reaction zone to reduce thepartial pressures of the reacted gases, i.e., hydrogen and carbonmonoxide.

Proportions of the reactants are not critical, although certainproportions may be optimum for a given ethylenically unsaturatedcompound, catalyst and solvent. Selection of optimum proportions will beobvious to one skilled in the art. In general, the amount of CO (basedon the moles of ethylenically unsaturated hydrocarbon) is preferablyfrom about 0.1 to 30 mole percent, the amount of NH (suppliedas a gas,as a liquid or as ammonium hydrocarbon) from about 0.1 to 95 molepercent and the amount of hydrogen from about 0.1 to 30 mole percent ofthe reactants.

The reaction is preferably conducted in the presence of a base and theammonia reactant is sufficient to provide such base. Other bases such asammonium hydroxide or the alkali metal and alkaline earth metalhydroxides, e.g., potassium hydroxide, calcium, hydroxide, strontiumhydroxide, are advantageously used. The amount of such base can be fromabout 0.01 to weight percent of the reaction medium.

The invention will be more specifically illustrated by the followingnon-limiting examples:

EXAMPLE 1 To a one-half gallon autoclave were added one-half gramsrhodium trichloride, 5 grams l,4-diazabicyclo(2.2.2)octane (DABCO), 5grams triphenylphosphine and 400 milliliters concentrated ammoniumhydroxide. The autoclave was pressured with ethylene to 200 atmospheres,carbon monoxide to 42 atmospheres, and hydrogen to 38 atmospheres. Themixture was mechanically stirred and heated to 100 C. for 2 hours, then200 C. for 2 hours. The final pressure was 29 atmospheres. There wasfound a milliliter organic layer which was shown to contain a mixture of3,5-dimethyl, 2-ethyl pyridine and 3,5-dimethyl, 4-ethyl pyridine in 54percent yield as deduced by preparative gas phase chromatography,infrared spectrum and nuclear magnetic resonance.

EXAMPLE 2 In a similar manner with 0.3 g rhodium trichloride, 3 g oftriphenylphosphine, 3 g of DABCO and g of ammonium acetate with 400 mlof concentrated ammonium hydroxide with ethylene to 400 psi, carbonmonoxide to 600 psi and hydrogen to 700 psi the mixture was stirred andheated to 100 C. for 2 hours, then 200 C. for 2 hours. There was a 37 gweight increase of which 50 percent was a mixture of dimethyl ethylpyridines as in Example 1. The autoclave was cleaned with aqua regia andwashed with water and acetone. The above run was repeated but noadditional rhodium was added. The product yield fell to 20 g weightincrease. Upon disassembly, a visual inspection of the cleaned autoclaveshowed that rhodium had precipitated onto the walls and several runscould be repeated without using additional rhodium.

EXAMPLE 3 To 5 g triphenylphosphine, 10 g sodium hydroxide and 400 ml ofconcentrated ammonium hydroxide in the conditioned autoclave fromExample 2 were added ethylene l to 400 psi, carbon monoxide to 700 psiand hydrogen to 1,000 psi. The mixture was stirred and heated to 100 C.for 2 hours. There was a 70 g weight increase of which 35 percent wasdimethyl ethyl pyridines as in Example I and 16 percent was 2(lmethyl-1butenyl)3,5-dimethyl pyridine.

To 0. 1 g bis(triphenylphosphine)carbonylrhodium(l)chloride, 5 gtriphenylphosphine, 300 ml pyridine and 142 g ammonia were addedethylene to 400 psi, carbon monoxide to 700 psi and hydrogen to 1,000psi. The mixture was stirred and heated to 100 C. for 2 hours. Thereaction was quite exothermic and there was an 80 g weight increase.

EXAMPLE 4 To 0. l g bis( triphenylphosphine )carbonylrhdoium(l)chloride,3 g triphenylphosphine, 300 ml tertiary amyl alcohol, 2 g sodiumhydroxide and 155 g of ammonia were added ethylene to 400 psi, carbonmonoxide to 700 psi and hydrogen to 1,200 psi. The mixture was stirredand heated to C. for 2 hours. There was a 92 g weight increase andpropionaldehyde, 2-methylpentenal and the dimethyl ethyl pyridines ofExample 1 were found.

I claim:

1. A process for the production of an R R R and Rhydrocarbyl-substituted pyridine comprising reacting an ethylenicallyunsaturated hydrocarbon having two to 24 carbons and having thestructure:

wherein R R R and R are the same or different univalent radicalsselected from hydrogen, alkyl, arylalkyl, cycloalkyl alkylcycloalkyl,aryl, or alkylaryl, or wherein one of said R or R groups together withone of said R and R groups together form an alkylene group resulting ina cycloalkene having four to 10 cyclic carbons; carbon monoxide; ammoniaand hydrogen in a liquid medium comprising an inert solvent or from 30to 100 percent excess of said ammonia, olefin or ammonium hydroxide andcontaining 0.00l-5 weight percent of a Group VIII noble metal in complexassociation with 0.002 to 10 weight percent of a biphyllic ligand havingat least three carbons and having the structure:

wherein E is trivalent phosphorus, arsenic or antimony;

R is hydrogen, alkyl having from one to 10 carbons, cycloalkyl havingfrom four to 10 carbons, or phenyl or a halo methyl, amino, or alkoxysubstitution product thereof having six to 10 carbons; and

R is alkylene having one to eight carbons; said reaction being conductedat a temperature of 50 to 400 C. and a pressure of 5 to 300 atmospheressufiicient to maintain liquid phase.

2. The process of claim 1 in which the Group VIII noble metal isrhodium.

3. The process of claim 1 in which the ethylenically unsaturatedhydrocarbon is an alpha alkene having two to 18 carbons.

4. The process of claim 3 in which the alkene is ethylene.

5. The process of claim 1 in which the noble metal is supplied to thereaction medium as a salt soluble in the reaction medium to form saidcomplex in situ.

6. The process of claim 1 in which the biphyllic ligand istriphenylphosphine.

7. The process of claim 2 wherein the catalyst is formed by addingrhodium trichloride to the reaction medium and wherein at least one ofthe R groups of said biphyllic ligand is phenyl.

8. The process of claim 1 in which the reaction medium contains 0.001 to10 weight percent of a bior tri-heterocyclic saturated amine having atleast one nitrogen in the bridgehead position and having 2 to 10 carbonsand 1 to 2 heterocyclic nitrogens.

9. The process of claim 8 wherein said amine is bicyclic.

10. The process of claim 9 in which the amine is1,4-diazabicyclo(2.2.2)octane.

11. The process of claim 9 wherein said catalyst is rhodium in complexassociation with triphenylphosphine.

12. The process of claim 11 wherein said ethylenically unsaturatedhydrocarbon is an alpha alkene having 2 to 18 carbons.

13. The process of claim 12 wherein said alkene is ethylene.

2. The process of claim 1 in which the Group VIII noble metal isrhodium.
 3. The process of claim 1 in which the ethylenicallyunsaturated hydrocarbon is an alpha alkene having two to 18 carbons. 4.The process of claim 3 in which the alkene is ethylene.
 5. The processof claim 1 in which the noble metal is supplied to the reaction mediumas a salt soluble in the reaction medium to form said complex in situ.6. The process of claim 1 in which the biphyllic ligand istriphenylphosphine.
 7. The process of claim 2 wherein the catalyst isformed by adding rhodium trichloride to the reaction medium and whereinat least one of the R groups of said biphyllic ligand is phenyl.
 8. Theprocess of claim 1 in which the reaction medium contains 0.001 to 10weight percent of a bi- or tri-heterocyclic saturated amine having atleast one nitrogen in the bridgehead position and having 2 to 10 carbonsand 1 to 2 heterocyclic nitrogens.
 9. The process of claim 8 whereinsaid amine is bicyclic.
 10. The process of claim 9 in which the amine is1,4-diazabicyclo(2.2.2)octane.
 11. The process of claim 9 wherein saidcatalyst is rhodium in complex association with triphenylphosphine. 12.The process of claim 11 wherein said ethylenically unsaturatedhydrocarbon is an alpha alkene having 2 to 18 carbons.
 13. The processof claim 12 wherein said alkene is ethylene.